CN111285409A - Gas-sensitive nanomaterial based on single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure, preparation process and application thereof - Google Patents
Gas-sensitive nanomaterial based on single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure, preparation process and application thereof Download PDFInfo
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- 239000002356 single layer Substances 0.000 title claims abstract description 50
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 39
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002073 nanorod Substances 0.000 title claims abstract description 35
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 239000004793 Polystyrene Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 15
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007667 floating Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 43
- 239000004065 semiconductor Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical group [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a gas-sensitive nanomaterial based on a single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure, and a preparation process and application thereof. According to the invention, the single-layer tin oxide nanometer bowl material is prepared by adopting a hard template method with simple synthesis conditions, and then the branched iron oxide nanorod is prepared by adopting a hydrothermal method, so that the single-layer tin oxide nanometer bowl branched iron oxide nanorod multistage heterostructure is finally obtained. Compared with the existing preparation process, the method has the advantages of strong repeatability, high yield, high preparation efficiency, large-scale production, compatibility with the silicon integrated circuit process and the like. The multistage composite nanostructure based on the heterojunction, which is constructed by the invention, has the advantages that the sensitivity is greatly improved when the multistage composite nanostructure is applied to gas sensing, the response time and the recovery time are greatly shortened, and the excellent gas-sensitive performance is shown; the method can realize ultrasensitive and high-selectivity detection on the trace formaldehyde, and provides a solid technical support for developing a high-sensitivity and high-stability gas sensor in the field of gas monitoring.
Description
Technical Field
The invention relates to the technical field of semiconductor nano material preparation, in particular to a gas-sensitive nano material based on a single-layer ordered tin oxide nano bowl branched iron oxide nanorod structure, which has high specific surface area, high sensitivity and excellent stability, a preparation process and application thereof.
Background
In recent years, a resistance type gas sensor based on a semiconductor nanomaterial has received great attention, and has been widely used in various fields such as gas leakage alarm, environmental gas monitoring, and industrial gas analysis. The development of various novel gas sensors based on metal oxide semiconductor materials, which have high specific surface area, excellent gas adsorption capacity and high carrier mobility, has become a current research hotspot. The formaldehyde gas belongs to a class of carcinogens, is widely present in indoor decoration materials, and has great influence on human health in life. A novel formaldehyde gas sensor with high sensitivity, quick response-recovery and low power consumption is developed, and the human body can be effectively protected from the influence of formaldehyde. Currently, gas sensors are of various types, including electrochemical, semiconductor chemiresistor, and PID, among others, based on the chemistry of MEMS technology
Resistive gas sensors have received great attention due to their advantages of small size, low power consumption, integratability, etc. The development of a highly efficient gas sensitive material is the key to determining the performance of MEMS-based gas sensors. Since the nano material has an ultra-high specific surface area, a small size effect, etc., it tends to exhibit more excellent gas sensing performance than other materials when used as a gas sensitive material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a gas-sensitive nanomaterial based on a single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure, a preparation process and application thereof. The single-layer ordered tin oxide nanometer bowl branched iron oxide nanometer rod material prepared by the invention has the characteristics of high specific surface area, high sensitivity, high selectivity and excellent stability as a gas sensitive material, and can be used for selective detection of trace formaldehyde.
The invention provides a preparation process of a gas-sensitive nano material based on a single-layer ordered tin oxide nano bowl branched iron oxide nano rod structure, which adopts a hard template method with simple synthesis conditions to prepare the single-layer ordered tin oxide nano bowl material and adopts a hydrothermal method to synthesize a branched iron oxide nano rod; the method comprises the following specific steps:
(1) taking PS (polystyrene) balls or PMMA (polymethyl methacrylate) ball powder with the diameter of less than 1 mu m, carrying out ultrasonic dispersion by using deionized water to prepare a dispersion liquid with the mass fraction of 1-4 wt%, and adding absolute ethyl alcohol to dilute the obtained dispersion liquid by 1-2 times;
(2) preparing a stannic chloride precursor solution for preparing the monolayer tin oxide nanometer bowl, wherein the concentration of the stannic chloride solution is 0.05-0.20 mol/L;
(3) dropwise adding the dispersed solution of the PS balls or the PMMA balls diluted by the absolute ethyl alcohol prepared in the step (1) into the precursor solution of the stannic chloride prepared in the step (2), and then dropwise adding a few drops of a surfactant to obtain single-layer PS balls or PMMA balls floating on the surface of the precursor solution;
(4) fishing the single-layer PS balls or PMMA balls floating on the surface of the precursor solution in the step (3) by using the cleaned substrate, and putting the sample into a muffle furnace for calcination after the single-layer PS balls or PMMA balls are completely dried at room temperature or in an oven; after calcining and sintering, naturally cooling to room temperature to obtain a single-layer tin oxide nano bowl structure;
(5) and (3) placing the sample obtained in the step (4) into a hydrothermal kettle, adding a mixed solution containing ferric chloride and sodium nitrate into the hydrothermal kettle, generating a branched ferric oxide nanorod structure by a hydrothermal method, washing with deionized water after the branched ferric oxide nanorod structure is generated, and drying to obtain the multi-stage heterogeneous gas-sensitive nanomaterial of the single-layer tin oxide nanometer bowl branched ferric oxide nanorod.
In the step (3), the surfactant is sodium dodecyl sulfate; after the surfactant is dropped, the single-layer ordered PS spheres or PMMA spheres which are closely arranged (such as hexagonal close packing) and float on the surface of the stannic chloride solution can be obtained.
In the step (4), different substrates can be selected according to requirements, and the substrate is a silicon wafer, a quartz wafer or other substrates.
In the step (4), when the drying oven is used for drying, the setting temperature of the drying oven is not higher than 80 ℃, and preferably 60-80 ℃.
In the step (4), the calcining temperature of the muffle furnace is 450-600 ℃, and the calcining time is 1-3 h.
In the step (5), the concentration of ferric chloride is 0.02-0.10 mol/L and the concentration of sodium nitrate is 0.5-1.5 mol/L in the mixed solution; the hydrothermal growth temperature is 100-110 ℃, and the growth time is 15-60 minutes.
The invention also provides a gas-sensitive nanomaterial based on a single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure, which is prepared by the preparation process. The average pore diameter of the multi-stage heterogeneous gas-sensitive nano material with the single-layer ordered tin oxide nano bowl branched iron oxide nanorod structure is determined by the diameter of a PS (polystyrene) sphere or a PMMA (polymethyl methacrylate) sphere of a hard template, and the average diameter of the branched nanorod is about 100-500 nm.
The invention further provides application of the gas-sensitive nanomaterial based on the single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure in detecting organic volatile gas, in particular application in selectively detecting formaldehyde.
Compared with the prior art, the invention has the beneficial effects that:
1. the multistage nano structure based on the heterojunction is constructed, compared with a single tin oxide structure, the sensitivity is greatly improved when the multistage nano structure is applied to gas sensing, the response time and the recovery time are greatly shortened, and more excellent gas-sensitive performance is shown.
2. Compared with a thin film structure, the single-layer ordered nano bowl structure effectively increases the specific surface area of the material, and the branched nanorod structure further increases the specific surface area, so that the gas-sensitive performance of the material can be effectively improved.
3. The multi-stage heterogeneous gas-sensitive nano material with the single-layer ordered tin oxide nano bowl branched iron oxide nanorod structure can realize ultra-sensitive and high-selectivity detection on trace formaldehyde, can detect organic volatile gas in a trace manner, and provides a solid technical support for developing a high-sensitivity and high-stability gas sensor in the field of gas monitoring.
4. The preparation process combines a hydrothermal method and a hard template method with simple synthesis conditions, can realize large-scale preparation on various substrates, and has the advantages of strong repeatability, high yield, high preparation efficiency, suitability for large-scale preparation, compatibility with silicon substrates and the like compared with the traditional preparation process.
Drawings
FIG. 1 is a flow diagram of a preparation process of a multi-stage heterogeneous gas-sensitive nanomaterial based on a single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure.
FIG. 2 is an SEM representation of the monolayer ordered tin oxide nanobowl obtained in example 1.
FIG. 3 is an SEM representation of the monolayer ordered tin oxide nanobowl-branched iron oxide nanorods obtained in example 1.
FIG. 4 is a TEM representation of the monolayer ordered tin oxide nanobowl-branched iron oxide nanorods obtained in example 1.
Fig. 5 is a trace formaldehyde gas-sensitive performance test result diagram of the two devices of the single-layer ordered tin oxide nano bowl and the single-layer ordered tin oxide nano bowl branched iron oxide nano rod obtained in example 1.
FIG. 6 is a graph of the results of the selective gas-sensitive test of the single-layer ordered tin oxide nanobowl-branched iron oxide nanorods to five reducing gases, obtained in example 1.
FIG. 7 is an SEM representation of the monolayer ordered tin oxide nanobowl-branched iron oxide nanorods obtained in example 2.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
The flow block diagram of the preparation process of the multilevel heterogeneous gas-sensitive nanomaterial based on the single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure is shown in figure 1.
Example 1
(1) Taking PS ball dispersion liquid with the diameter of 800 nm and the mass fraction of 2 wt%, and adding absolute ethyl alcohol to dilute by 1 time;
(2) preparing a stannic chloride solution with the concentration of 0.15 mol/L;
(3) dropwise adding 0.15 mol/L stannic chloride solution into PS sphere dispersion liquid diluted by absolute ethyl alcohol, and then adding 1 drop of surfactant to obtain a single-layer PS sphere floating on the surface of the stannic chloride solution;
(4) fishing out the single-layer PS ball by using a silicon wafer with an interdigital electrode, and putting the sample into a muffle furnace to calcine for 2 hours at 500 ℃ after the single-layer PS ball is completely dried at room temperature; after calcining and sintering, naturally cooling to room temperature;
(5) and (4) carrying out hydrothermal reaction on the sample obtained in the step (4) at 106 ℃ for 30 minutes to obtain branched iron oxide nanorods, washing with deionized water after the hydrothermal reaction is finished, and drying.
The sample obtained in the step (4) is in a single-layer ordered tin oxide nanometer bowl structure, and is specifically shown in figure 2; the structure of the sample obtained after the step (5) is shown in fig. 3 and fig. 4, and the result shows that branched iron oxide nanorods are generated around the nano bowl by a hydrothermal method, and the average diameter of the nanorods is between 100 nm and 400 nm.
The single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod MP-SnO obtained in the step (5) is utilized2@Fe2O3NRs and single-layer ordered tin oxide nanometer bowl MP-SnO2And carrying out gas sensing test on 750-150 ppb formaldehyde gas. For 750ppb of formaldehyde gas, MP-SnO2@Fe2O3Response value of NRs (defined as R)a/RgWherein R isaIs resistance in air, RgResistance in gas to be measured) is 1.62, and MP-SnO2The sensitivity of the branched nanorod structure is 0.12, the sensitivity of the branched nanorod structure disclosed by the invention to 750ppb formaldehyde gas is improved by 5 times, and the sensitivity of the branched nanorod structure to formaldehyde gas with other concentrations is also improved by 5 timesWith varying degrees of lift (as shown in figure 5). In addition, for the obtained MP-SnO2@Fe2O3NRs were tested for selectivity, i.e. gas sensitive measurements were performed on methane, nitrogen dioxide, acetone, toluene, hydrogen sulfide and ammonia, respectively, at the same concentrations (1 ppm). As shown in FIG. 6, the single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod MP-SnO of the invention2@Fe2O3NRs exhibit extremely excellent selectivity to formaldehyde gas.
Example 2
Similar to example 1, the difference is that the hydrothermal growth time for the branched iron oxide nanorods is 60 minutes. The SEM representation picture of the obtained monolayer ordered tin oxide nanometer bowl branched iron oxide nanometer rod is shown in figure 7.
The embodiments of the present invention have been described in detail in the above examples, but the present invention is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (9)
1. A preparation process of a gas-sensitive nanomaterial based on a single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure is characterized by comprising the following specific steps of:
(1) taking PS (polystyrene) balls or PMMA (polymethyl methacrylate) ball powder with the diameter of less than 1 mu m, carrying out ultrasonic dispersion by using deionized water to prepare a dispersion liquid with the mass fraction of 1-4 wt%, and adding absolute ethyl alcohol to dilute the obtained dispersion liquid by 1-2 times;
(2) preparing a stannic chloride precursor solution for preparing the monolayer tin oxide nanometer bowl, wherein the concentration of the stannic chloride solution is 0.05-0.20 mol/L;
(3) dropwise adding the dispersed solution of the PS balls or the PMMA balls diluted by the absolute ethyl alcohol prepared in the step (1) into the precursor solution of the stannic chloride prepared in the step (2), and then dropwise adding a few drops of a surfactant to obtain single-layer PS balls or PMMA balls floating on the surface of the precursor solution;
(4) fishing the single-layer PS balls or PMMA balls floating on the surface of the precursor solution in the step (3) by using the cleaned substrate, and putting the sample into a muffle furnace for calcination after the single-layer PS balls or PMMA balls are completely dried at room temperature or in an oven; after calcining and sintering, naturally cooling to room temperature to obtain a single-layer tin oxide nano bowl structure;
(5) and (3) placing the sample obtained in the step (4) into a hydrothermal kettle, adding a mixed solution containing ferric chloride and sodium nitrate into the hydrothermal kettle, generating a branched ferric oxide nanorod structure by a hydrothermal method, washing with deionized water after the branched ferric oxide nanorod structure is generated, and drying to obtain the multi-stage heterogeneous gas-sensitive nanomaterial of the single-layer ordered tin oxide nanometer bowl branched ferric oxide nanorod.
2. The process according to claim 1, wherein in the step (3), the surfactant is sodium lauryl sulfate.
3. The process according to claim 1, wherein in the step (4), the substrate is a silicon wafer or a quartz wafer.
4. The preparation process according to claim 1, wherein in the step (4), when the drying is performed by using an oven, the temperature of the oven is set to be 60-80 ℃.
5. The preparation process according to claim 1, wherein in the step (4), the muffle furnace is used for calcining at 450-600 ℃ for 1-3 h.
6. The preparation process according to claim 1, wherein in the step (5), the concentration of ferric chloride in the mixed solution is 0.02-0.10 mol/L ferric chloride and 0.5-1.5 mol/L sodium nitrate; the hydrothermal growth temperature is 100-110 ℃, and the growth time is 15-60 minutes.
7. The gas-sensitive nanomaterial based on the single-layer ordered tin oxide nanometer bowl branched iron oxide nanorod structure prepared by the preparation process of claim 1.
8. The gas-sensitive nanomaterial based on a monolayer ordered tin oxide nanobowl-branched iron oxide nanorod structure according to claim 7, comprising a monolayer ordered nanocowlike tin oxide and iron oxide nanorods branched around it; the average diameter of the iron oxide nano-rod is between 100 and 500 nm.
9. Use of the gas-sensitive nanomaterial based on the monolayer ordered tin oxide nanobowl-branched iron oxide nanorod structure of claim 7 or 8 in the aspect of formaldehyde detection.
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